Solution feed of multiple catalysts

ABSTRACT

This invention relates to methods to introduce multiple catalysts, activators or catalyst systems into a gas phase reactor.

FIELD OF THE INVENTION

This invention relates to a method to feed multiple catalysts systemsinto a polymerization reactor, preferably a gas or slurry phasepolymerization reactor.

BACKGROUND OF THE INVENTION

The demands of polyolefin fabricators are increasingly becoming more andmore specific. In an attempt to meet these demands polyolefin producersare attempting to create more and more specialized polyolefins that haveparticular product configurations. One means to do this comprises usingtwo catalysts in the same reactor to produce intimately mixed polymerblends. The difficulty however lies in selecting compatible catalyststhat will actually work together well and reactor conditions that do notbenefit one catalyst while hindering another.

Mobil, in PCT patent application WO 99/03899, discloses using ametallocene type catalyst and a Ziegler-Natta type catalyst in the samereactor to produce a bimodal molecular weight distribution (MWD)high-density polyethylene (HDPE). These two catalyst however were fedinto the reactor as supported powders.

U.S. Pat. Ser. No. 09/312,878 filed May 17, 1999 discloses a gas orslurry phase polymerization process using a supported bisamide catalyst.

SUMMARY OF THE INVENTION

This invention relates to a method to feed multiple catalysts systemsinto a polymerization reactor, preferably a gas or slurry phasepolymerization reactor. The catalysts, activators and/or catalystsystems are preferably introduced into the reactor in a liquid carrier,preferably in solution. The catalysts, activators, catalysts systems,etc may be combined in different orders and in different amounts. Theindividual catalysts or activators may be introduced into the reactordirectly or they may be combined with one or more other catalysts and oractivators prior to being placed in the reactor. Further the catalysts,activators and/or catalyst systems (and the carriers) may be contactedsequentially, in series or in parallel. Each catalyst, however, isindependently activated.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a graphic representation of Illustration 1 below.

FIG. 2 is a graphic representation of Illustration 2 below.

FIG. 3 is a graphic representation of Illustration 3 below.

FIG. 4 is a graphic representation of Illustration 4 below.

FIG. 5 is a graphic representation of Illustration 5 below.

FIG. 6 is a graphic representation of Illustration 6 below.

FIG. 7 is a graphic representation of Illustration 7 below.

FIG. 8 is a graphic representation of Illustration 8 below.

FIG. 9 is a graphic representation of Illustration 9 below.

DETAILED DESCRIPTION OF THE INVENTION

In a preferred embodiment this invention relates to a method tointroduce multiple catalysts, activators, or catalyst systems into apolymerization reactor, preferably a gas phase reactor. For the purposesof this invention the term “catalyst” refers to a metal compound thatwhen combined with an activator polymerizes olefins. For the purposes ofthis invention, the term “catalyst system” refers to the combination ofa catalyst and an activator. For the purposes of this invention the term“activator” is used interchangeably with the term “co-catalyst.”

The catalyst system(s), the catalysts and or the activators arepreferably introduced into the reactor in one or more liquid carriers,preferably as a solution, suspension or an emulsion. For example, in oneembodiment, a solution of two catalyst systems in an alkane such aspentane, hexane, toluene, isopentane or the like is introduced into thegas or slurry phase reactor. In another embodiment the catalyst oractivator or both are contacted in a liquid carrier with a surfactant toproduced an emulsion, then the emulsion is introduced into a reactor,such as for example, by spraying the emulsion into a particle lean zone.(Particle lean zones are described in U.S. Pat. No. 5,693,727,incorporated by reference herein.)

The catalysts, activators, catalysts systems, etc may be combined indifferent orders and in different amounts. In some embodiments the eachcatalyst may be contacted with the same or different activators.Likewise the catalysts may be contacted with each other first thencontacted with the activator(s). Similarly the activator may becontacted with one catalyst first with the second catalyst being addedthereafter. Further there may be time periods, anywhere from 1 second toseveral days or more between each of the contacts.

In the various activation and feed schemes possible in the practice ofthis invention it is particularly preferred that each catalyst beindependently activated. By independently activated is meant that eachcatalyst has an opportunity to combine or react with an activator withhaving to compete for activator with another catalyst. For example inone embodiment the two catalysts are activated in separate chambers thencombined before introduction into the reactor. In another embodiment afirst catalyst is activated with an activator, thereafter a secondcatalyst is added to the first catalysts/activator combination andallowed to react/combine with the excess activator. In this embodimentthe second catalyst is still activated independently from the first.Likewise in another embodiment two or more catalysts can be activatedindependently at the same time in the same solution as long assufficient activator for both catalysts to be activated.

In another particularly preferred embodiment, the various catalystcombinations are all combined prior to being introduced into thereactor. The catalyst combinations may be fed into the reactor frommultiple injection points, however it is preferred that the samecatalyst solution be fed into the reactor through all the injectionpoints.

In particular this invention relates to the following illustrations ofcombinations. In the following illustrations, A refers to a catalyst ormixture of catalysts, and B refers to a different catalyst or mixture ofcatalysts. The mixtures of catalysts in A and B can be the samecatalysts, just in different ratios. Graphic representations of thesesillustrations are FIGS. 1-9. Further, it is noted that additionalsolvents or inert gases may be added at many locations.

Illustration 1: A and B plus the activator are mixed off-line and thenfed to the reactor.

Illustration 2: A and B are mixed off-line. Activator is added on-lineand then fed to the reactor.

Illustration 3: A or B is contacted with the activator (off-line) andthen either A or B is added on-line before entering the reactor.

Illustration 4: A or B is contacted with the activator (on-line) andthen either A or B is added on-line before entering the reactor.

Illustration 5: A and B are each contacted with the activator off-line.Then A+activator and +cocatalyst are contacted on-line before enteringthe reactor.

Illustration 6: A and B are each contacted with the activator on-line.Then A+activator and B+activator are contacted on-line before enteringthe reactor. (This is a preferred configuration since the ratio of A toB and the ratio of activator to A and the ratio of activator to B can becontrolled independently.)

Illustration 7: In this example, A or B is contacted with the activator(on-line) while a separate solution of either A or B is contacted withactivator off-line. Then both stream of A or B+activator are contactedon-line before entering the reactor.

Illustration 8: A is contacted on-line with B. Then, an activator is fedto on-line to the A+B mixture.

Illustration 9: A is activated with activator off-line. Then A+activatoris contacted on-line with B. Then, an activator is fed to in-line to theA+B+activator mixture.

Illustration 10: A and B are mixed off-line. Then the mixture of Aand Bis contacted on-line with activator, then additional catalyst A is addedon line, thereafter additional catlayst B is added on-line and then thewhole mixture is introduced into the reactor.

In any of the above illustrations, a means for mixing and/or creating acertain residence time may be employed. For example a mixing blade orscrew may be used to mix the components or a certain length pipe may beused to obtain a desired contact or residence time between thecomponents.

“On-line” means the material described is in a pipe, tube, or vesselwhich is directly or indirectly connected to the reactor system.

“Off-line” means the material described is in a pipe, tube, or vesselwhich is not connected to the reactor system.

In a preferred embodiment this invention relates to a method topolymerize olefins in a gas-phase reactor wherein at least two catalystsand at least one activator are introduced in the polymerization reactorin a liquid carrier. In a preferred embodiment the catalysts and theactivator(s) are combined in the liquid carrier before being introducedinto the reactor.

In another preferred embodiment the catalysts are combined in a liquidcarrier then introduced into a channeling means connecting to thereactor and thereafter the activator(s) is introduced into thechanneling means at the same or different point as the catalysts.

In another preferred embodiment the catalysts are combined in a liquidcarrier and thereafter the activator(s) is introduced into the liquidcarrier.

In another preferred embodiment the liquid carrier containing thecatalysts and the activator(s) are placed into an apparatus forintroducing the liquid carrier into the reactor.

In another preferred embodiment the catalysts and liquid carrier areintroduced into the apparatus before the activator is introduced intothe apparatus.

In another preferred embodiment the composition comprising the liquidcarrier comprises a liquid stream flowing or sprayed into the reactor.

In another preferred embodiment at least one catalyst, at least oneactivator and the liquid carrier are placed into an apparatus forintroduction into the reactor wherein additional catalyst(s) is/areintroduced into the apparatus after the first catalyst and activator areintroduced into the apparatus.

In another preferred embodiment, a first combination comprising at leastone catalyst in a liquid carrier is introduced into an apparatusconnecting to the reactor, and a second composition comprising at leastone activator in liquid carrier is introduced into the apparatusconnecting to the reactor, then, after a period of time, a differentcatalyst in liquid carrier is introduced into the apparatus connectingto the reactor, and then the catalyst-activator combination isintroduced into the reactor.

In another preferred embodiment, at least one catalyst(a) and at leastone activator(a) are combined in a liquid carrier, and at least onecatalyst(b) and at least one activator(b) are combined in a liquidcarrier, wherein either the catalyst(b) is different from thecatalyst(a) or the activator (b) is different from the activator(a),thereafter both combinations are introduced into an apparatus connectingto the reactor, and, thereafter the combinations are introduced into thereactor.

In another preferred embodiment the liquid carrier containingcatalyst(b) and activator(b) is introduced into the apparatus connectingto the reactor after the liquid carrier containing catalyst(a) andactivator(a) is introduced into the apparatus connecting to the reactor.

In another preferred embodiment, a first composition comprising at leastone catalyst(a), at least one activator(a) and a liquid carrier isplaced in an apparatus connected to the reactor, and a secondcomposition comprising at least one catalyst(b), at least oneactivator(b) and a liquid carrier, wherein either the catalyst(b) or theactivator (b) is different from the catalyst(a) or the activator(a), isintroduced into the apparatus connecting to the reactor after the firstcomposition is, and thereafter the combined compositions is introducedinto the reactor.

In another preferred embodiment at least one catalyst and the liquidcarrier are placed into an apparatus for introduction into the reactorwherein additional catalyst(s) and activator(s) are introduced into theapparatus after the first catalyst is introduced into the apparatus.

In another preferred embodiment a first composition comprising at leastone catalyst(a), at least one activator(a) and a liquid carrier isintroduced into an apparatus feeding into a reactor, and thereafter asecond catalyst in a liquid carrier is added to the apparatus feedinginto the reactor, and thereafter a second activator in a liquid carrieris added to the apparatus feeding into the reactor, and thereafter thetotal combination is introduced into the reactor.

More specific preferred embodiments include:

1. Catalyst A could be used as a 0.25 weight % solution in hexane andCatalyst B could be used as a 0.50 weight % solution in toluene at molarratios of B to A of about 0.7 when the two are activated separately thenmixed together or at molar ratios of B to A of 2.2 to 1.5 when A isactivated then B is added.

2. Raising or lowering the reaction temperature to narrow or broaden theMw/Mn, respectively.

3. Changing residence time to affect product properties. Large changescan have significant impact. One to five, preferably four hoursresidence time appears to produce good product properties.

4. Spraying the catalyst into the reactor in such a way as to create aparticle lean zone. A particle lean zone can be created by a 50,000lb/hr flow of cycle gas through 6 inch pipe. The catalyst can beatomized w/ a spray nozzle using nitrogen atomizing gas.

5. The activator, preferably MMAO 3A can be used at 7 weight % al inisopentane, hexane or heptane at feed rate sufficient to give an Al/Zrratio of 100 to 300.

6. Catalyst A is mixed on-line with MMAO 3A then Catalyst B is added online, then the mixture is introduced into the reactor.

7. Catalyst A is mixed on-line with MMAO 3A and Catalyst B is mixed online with MMAO 3A thereafter the two activated catalysts are mixedon-line then introduced into the reactor.

In a preferred embodiment Catalyst A is Compound I (as described below)and Catalyst B is indenyl zirconium tris pivalate.

In one embodiment, a second catalyst is contacted with the firstcatalyst and activator, such as modified methylalumoxane, in a solventand just before the solution is fed into a gas or slurry phase reactor.In another embodiment a solution of a first catalyst is combined with asolution of the second catalyst and the activator then introduced intothe reactor.

In another embodiment, two or more catalysts are blended together in aslurry feed vessel then are contacted with one or more activators,allowed to react for a specified amount of time then introduced into thereactor. In another embodiment two or more catalysts are contactedin-line and then the activator is fed into the combined stream thenintroduced into the reactor. In another embodiment the catalysts areindependently activated in-line and then contacted just before deliveryto the reactor. Intimate mixing of the catalysts and/or the activator ispreferred. A static mixer can be used to achieve intimate mixing. Inanother embodiment the a dilute solution of catalyst is added to apre-mixed batch of catalysts.

Solutions of the catalysts are prepared by taking the catalyst anddissolving it in any solvent such as a hydrocarbon, preferably analkane, toluene, xylene, etc. The solvent may first be purified in orderto remove any poisons which may affect the catalyst activity, includingany trace water and/or oxygenated compounds. Purification of the solventmay be accomplished by using activated alumina and/or activatedsupported copper catalyst, for example. The catalyst is preferablycompletely dissolved into the solution to form a homogeneous solution.Both catalysts may be dissolved into the same solvent, if desired. Oncethe catalysts are in solution, they may be stored indefinitely untiluse. Preferred solvents include pentane, hexane, butane, isopentane,cyclohexane, toluene, xylene, and the like.

Catalysts

One of many catalysts or catalysts systems that may be used hereininclude a group 15 containing metal compound as described below. Othercatalysts that may be used include transition metal catalysts notincluded in the description above such as one or more bulky ligandmetallocene-type catalysts and/or one or more conventional typetransition metal catalysts such as one or more Ziegler-Natta catalysts,vanadium catalysts and/or chromium catalysts.

For purposes of this invention cyclopentadienyl group is defined toinclude indenyls and fluorenyls.

Group 15 Containing Metal Compound

The mixed catalyst composition of the present invention includes a Group15 containing metal compound. The Group 15 containing compound generallyincludes a Group 3 to 14 metal atom, preferably a Group 3 to 7, morepreferably a Group 4 to 6, and even more preferably a Group 4 metalatom, bound to at least one leaving group and also bound to at least twoGroup 15 atoms, at least one of which is also bound to a Group 15 or 16atom through another group.

In one preferred embodiment, at least one of the Group 15 atoms is alsobound to a Group 15 or 16 atom through another group which may be a C₁to C₂₀ hydrocarbon group, a heteroatom containing group, silicon,germanium, tin, lead, or phosphorus, wherein the Group 15 or 16 atom mayalso be bound to nothing or a hydrogen, a Group 14 atom containinggroup, a halogen, or a heteroatom containing group, and wherein each ofthe two Group 15 atoms are also bound to a cyclic group and mayoptionally be bound to hydrogen, a halogen, a heteroatom or ahydrocarbyl group, or a heteroatom containing group.

In a preferred embodiment, the Group 15 containing metal compound of thepresent invention may be represented by the formulae:

wherein M is a Group 3 to 12 transition metal or a Group 13 or 14 maingroup metal, preferably a Group 4, 5, or 6 metal, and more preferably aGroup 4 metal, and most preferably zirconium, titanium or hafnium, eachX is independently a leaving group, preferably, an anionic leavinggroup, and more preferably hydrogen, a hydrocarbyl group, a heteroatomor a halogen, and most preferably an alkyl. y is 0 or 1 (when y is 0group L′ is absent), n is the oxidation state of M, preferably +3, +4,or +5, and more preferably +4, m is the formal charge of the YZL or theYZL′ ligand, preferably 0, −1, −2 or −3, and more preferably −2, L is aGroup 15 or 16 element, preferably nitrogen, L′ is a Group 15 or 16element or Group 14 containing group, preferably carbon, silicon orgermanium, Y is a Group 15 element, preferably nitrogen or phosphorus,and more preferably nitrogen, Z is a Group 15 element, preferablynitrogen or phosphorus, and more preferably nitrogen, R¹ and R² areindependently a C₁ to C₂₀ hydrocarbon group, a heteroatom containinggroup having up to twenty carbon atoms, silicon, germanium, tin, lead,or phosphorus, preferably a C₂ to C₂₀ alkyl, aryl or aralkyl group, morepreferably a linear, branched or cyclic C₂ to C₂₀ alkyl group, mostpreferably a C₂ to C₆ hydrocarbon group. R³ is absent or a hydrocarbongroup, hydrogen, a halogen, a heteroatom containing group, preferably alinear, cyclic or branched alkyl group having 1 to 20 carbon atoms, morepreferably R³ is absent, hydrogen or an alkyl group, and most preferablyhydrogen R⁴ and R⁵ are independently an alkyl group, an aryl group,substituted aryl group, a cyclic alkyl group, a substituted cyclic alkylgroup, a cyclic aralkyl group, a substituted cyclic aralkyl group ormultiple ring system, preferably having up to 20 carbon atoms, morepreferably between 3 and 10 carbon atoms, and even more preferably a C₁to C₂₀ hydrocarbon group, a C₁ to C₂₀ aryl group or a C₁, to C₂₀ aralkylgroup, or a heteroatom containing group, for example PR₃, where R is analkyl group, R¹ and R² may be interconnected to each other, and/or R⁴and R⁵ may be interconnected to each other, R⁶ and R⁷ are independentlyabsent, or hydrogen, an alkyl group, halogen, heteroatom or ahydrocarbyl group, preferably a linear, cyclic or branched alkyl grouphaving 1 to 20 carbon atoms, more preferably absent, and R* is absent,or is hydrogen, a Group 14 atom containing group, a halogen, aheteroatom containing group.

By “formal charge of the YZL or YZL′ ligand”, it is meant the charge ofthe entire ligand absent the metal and the leaving groups X.

By “R¹ and R² may also be interconnected” it is meant that R¹ and R² maybe directly bound to each other or may be bound to each other throughother groups. By “R⁴ and R⁵ may also be interconnected” it is meant thatR⁴ and R⁵ may be directly bound to each other or may be bound to eachother through other groups.

An alkyl group may be a linear, branched alkyl radicals, or alkenylradicals, alkynyl radicals, cycloalkyl radicals or aryl radicals, acylradicals, aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthioradicals, dialkylamino radicals, alkoxycarbonyl radicals,aryloxycarbonyl radicals, carbomoyl radicals, alkyl- ordialkyl-carbamoyl radicals, acyloxy radicals, acylamino radicals,aroylamino radicals, straight, branched or cyclic, alkylene radicals, orcombination thereof. An aralkyl group is defined to be a substitutedaryl group.

In a preferred embodiment R⁴ and R⁵ are independently a grouprepresented by the following formula:

wherein R⁸ to R¹² are each independently hydrogen, a C₁ to C₄₀ alkylgroup, a halide, a heteroatom, a heteroatom containing group containingup to 40 carbon atoms, preferably a C₁ to C₂₀ linear or branched alkylgroup, preferably a methyl, ethyl, propyl or butyl group, any two Rgroups may form a cyclic group and/or a heterocyclic group. The cyclicgroups may be aromatic. In a preferred embodiment R⁹, R¹⁰ and R¹² areindependently a methyl, ethyl, propyl or butyl group (including allisomers), in a preferred embodiment R⁹, R¹⁰ and R¹² are methyl groups,and R⁸ and R¹¹ are hydrogen.

In a particularly preferred embodiment R⁴ and R⁵ are both a grouprepresented by the following formula:

In this embodiment, M is a Group 4 metal, preferably zirconium, titaniumor hafnium, and even more preferably zirconium; each of L, Y, and Z isnitrogen; each of R¹ and R² is —CH₂—CH₂—; R³ is hydrogen; and R⁶ and R⁷are absent.

In a particularly preferred embodiment the Group 15 containing metalcompound is represented by the formula:

In compound I, Ph equals phenyl.

The Group 15 containing metal compounds of the invention are prepared bymethods known in the art, such as those disclosed in EP 0 893 454 A1,U.S. Pat. No. 5,889,128 and the references cited in U.S. Pat. No.5,889,128 which are all herein incorporated by reference. U.S.application Ser. No. 09/312,878, filed May 17, 1999, discloses a gas orslurry phase polymerization process using a supported bisamide catalyst,which is also incorporated herein by reference.

A preferred direct synthesis of these compounds comprises reacting theneutral ligand, (see for example YZL or YZL′ of formula 1 or 2) withM^(n)X_(n) (M is a Group 3 to 14 metal, n is the oxidation state of M,each X is an anionic group, such as halide, in a non-coordinating orweakly coordinating solvent, such as ether, toluene, xylene, benzene,methylene chloride, and/or hexane or other solvent having a boilingpoint above 60° C., at about 20 to about 150° C. (preferably 20 to 100°C.), preferably for 24 hours or more, then treating the mixture with anexcess (such as four or more equivalents) of an alkylating agent, suchas methyl magnesium bromide in ether. The magnesium salts are removed byfiltration, and the metal complex isolated by standard techniques.

In one embodiment the Group 15 containing metal compound is prepared bya method comprising reacting a neutral ligand, (see for example YZL orYZL′ of formula 1 or 2) with a compound represented by the formulaM^(n)X_(n) (where M is a Group 3 to 14 metal, n is the oxidation stateof M, each X is an anionic leaving group) in a non-coordinating orweakly coordinating solvent, at about 20° C. or above, preferably atabout 20 to about 100° C., then treating the mixture with an excess ofan alkylating agent, then recovering the metal complex. In a preferredembodiment the solvent has a boiling point above 60° C., such astoluene, xylene, benzene, and/or hexane. In another embodiment thesolvent comprises ether and/or methylene chloride, either beingpreferable.

Bulky Ligand Metallocene-Type Compound

Bulky ligand metallocene-type compound (hereinafer also referred to asmetallocenes) may also be used in the practice of this invention.

Generally, bulky ligand metallocene-type compounds include half and fullsandwich compounds having one or more bulky ligands bonded to at leastone metal atom. Typical bulky ligand metallocene-type compounds aregenerally described as containing one or more bulky ligand(s) and one ormore leaving group(s) bonded to at least one metal atom. In onepreferred embodiment, at least one bulky ligands is η-bonded to themetal atom, most preferably η⁵-bonded to the metal atom.

The bulky ligands are generally represented by one or more open,acyclic, or fused ring(s) or ring system(s) or a combination thereof.These bulky ligands, preferably the ring(s) or ring system(s) aretypically composed of atoms selected from Groups 13 to 16 atoms of thePeriodic Table of Elements, preferably the atoms are selected from thegroup consisting of carbon, nitrogen, oxygen, silicon, sulfur,phosphorous, germanium, boron and aluminum or a combination thereof.Most preferably the ring(s) or ring system(s) are composed of carbonatoms such as but not limited to those cyclopentadienyl ligands orcyclopentadienyl-type ligand structures or other similar functioningligand structure such as a pentadiene, a cyclooctatetraendiyl or animide ligand. The metal atom is preferably selected from Groups 3through 15 and the lanthanide or actinide series of the Periodic Tableof Elements. Preferably the metal is a transition metal from Groups 4through 12, more preferably Groups 4, 5 and 6, and most preferably thetransition metal is from Group 4.

In one embodiment, the bulky ligand metallocene-type catalyst compoundsare represented by the formula:

L^(A)L^(B)MQ_(n)  (III)

where M is a metal atom from the Periodic Table of the Elements and maybe a Group 3 to 12 metal or from the lanthanide or actinide series ofthe Periodic Table of Elements, preferably M is a Group 4, 5 or 6transition metal, more preferably M is a Group 4 transition metal, evenmore preferably M is zirconium, hafnium or titanium. The bulky ligands,L^(A) and L^(B), are open, acyclic or fused ring(s) or ring system(s)and are any ancillary ligand system, including unsubstituted orsubstituted, cyclopentadienyl ligands or cyclopentadienyl-type ligands,heteroatom substituted and/or heteroatom containingcyclopentadienyl-type ligands. Non-limiting examples of bulky ligandsinclude cyclopentadienyl ligands, cyclopentaphenanthreneyl ligands,indenyl ligands, benzindenyl ligands, fluorenyl ligands,octahydrofluorenyl ligands, cyclooctatetraendiyl ligands,cyclopentacyclododecene ligands, azenyl ligands, azulene ligands,pentalene ligands, phosphoyl ligands, phosphinimine (WO 99/40125),pyrrolyl ligands, pyrozolyl ligands, carbazolyl ligands, borabenzeneligands and the like, including hydrogenated versions thereof, forexample tetrahydroindenyl ligands. In one embodiment, L^(A) and L^(B)may be any other ligand structure capable of η-bonding to M, preferablyη³-bonding to M and most preferably η⁵-bonding. In yet anotherembodiment, the atomic molecular weight (MW) of L^(A) or L^(B) exceeds60 a.m.u., preferably greater than 65 a.m.u. In another embodiment,L^(A) and L^(B) may comprise one or more heteroatoms, for example,nitrogen, silicon, boron, germanium, sulfur and phosphorous, incombination with carbon atoms to form an open, acyclic, or preferably afused, ring or ring system, for example, a hetero-cyclopentadienylancillary ligand. Other L^(A) and L^(B) bulky ligands include but arenot limited to bulky amides, phosphides, alkoxides, aryloxides, imides,carbolides, borollides, porphyrins, phthalocyanines, corrins and otherpolyazomacrocycles. Independently, each L^(A) and L^(B) may be the sameor different type of bulky ligand that is bonded to M. In one embodimentof formula (III) only one of either L^(A) or L^(B) is present.

Independently, each L^(A) and L^(B) may be unsubstituted or substitutedwith a combination of substituent groups R. Non-limiting examples ofsubstituent groups R include one or more from the group selected fromhydrogen, or linear, branched alkyl radicals, or alkenyl radicals,alkynyl radicals, cycloalkyl radicals or aryl radicals, acyl radicals,aroyl radicals, alkoxy radicals, aryloxy radicals, alkylthio radicals,dialkylamino radicals, alkoxycarbonyl radicals, aryloxycarbonylradicals, carbomoyl radicals, alkyl- or dialkyl-carbamoyl radicals,acyloxy radicals, acylamino radicals, aroylamino radicals, straight,branched or cyclic, alkylene radicals, or combination thereof. In apreferred embodiment, substituent groups R have up to 50 non-hydrogenatoms, preferably from 1 to 30 carbon, that can also be substituted withhalogens or heteroatoms or the like. Non-limiting examples of alkylsubstituents R include methyl, ethyl, propyl, butyl, pentyl, hexyl,cyclopentyl, cyclohexyl, benzyl or phenyl groups and the like, includingall their isomers, for example tertiary butyl, isopropyl, and the like.Other hydrocarbyl radicals include fluoromethyl, fluroethyl,difluroethyl, iodopropyl, bromohexyl, chlorobenzyl and hydrocarbylsubstituted organometalloid radicals including trimethylsilyl,trimethylgermyl, methyldiethylsilyl and the like; andhalocarbyl-substituted organometalloid radicals includingtris(trifluoromethyl)-silyl, methyl-bis(difluoromethyl)silyl,bromomethyldimethylgermyl and the like; and disubstitiuted boronradicals including dimethylboron for example; and disubstitutedpnictogen radicals including dimethylamine, dimethylphosphine,diphenylamine, methylphenylphosphine, chalcogen radicals includingmethoxy, ethoxy, propoxy, phenoxy, methylsulfide and ethylsulfide.Non-hydrogen substituents R include the atoms carbon, silicon, boron,aluminum, nitrogen, phosphorous, oxygen, tin, sulfur, germanium and thelike, including olefins such as but not limited to olefinicallyunsaturated substituents including vinyl-terminated ligands, for examplebut-3-enyl, prop-2-enyl, hex-5-enyl and the like. Also, at least two Rgroups, preferably two adjacent R groups, are joined to form a ringstructure having from 3 to 30 atoms selected from carbon, nitrogen,oxygen, phosphorous, silicon, germanium, aluminum, boron or acombination thereof. Also, a substituent group R group such as 1-butanylmay form a carbon sigma bond to the metal M.

Other ligands may be bonded to the metal M, such as at least one leavinggroup Q. In one embodiment, Q is a monoanionic labile ligand having asigma-bond to M. Depending on the oxidation state of the metal, thevalue for n is 0, 1 or 2 such that formula (III) above represents aneutral bulky ligand metallocene-type catalyst compound.

Non-limiting examples of Q ligands include weak bases such as amines,phosphines, ethers, carboxylates, dienes, hydrocarbyl radicals havingfrom 1 to 20 carbon atoms, hydrides or halogens and the like or acombination thereof. In another embodiment, two or more Q's form a partof a fused ring or ring system. Other examples of Q ligands includethose substituents for R as described above and including cyclobutyl,cyclohexyl, heptyl, tolyl, trifluromethyl, tetramethylene,pentamethylene, methylidene, methyoxy, ethyoxy, propoxy, phenoxy,bis(N-methylanilide), dimethylamide, dimethylphosphide radicals and thelike.

The two L groups may be bridged together by group A as defined below.

In one embodiment, the bulky ligand metallocene-type catalyst compoundsof the invention include those of formula (III) where L^(A) and L^(B)are bridged to each other by at least one bridging group, A, such thatthe formula is represented by

L^(A)L^(B)MQ_(n)  (IV)

These bridged compounds represented by formula (IV) are known asbridged, bulky ligand metallocene-type catalyst compounds. L^(A), L^(B),M, Q and n are as defined above. Non-limiting examples of bridging groupA include bridging groups containing at least one Group 13 to 16 atom,often referred to as a divalent moiety such as but not limited to atleast one of a carbon, oxygen, nitrogen, silicon, aluminum, boron,germanium and tin atom or a combination thereof. Preferably bridginggroup A contains a carbon, silicon or germanium atom, most preferably Acontains at least one silicon atom or at least one carbon atom. Thebridging group A may also contain substituent groups R as defined aboveincluding halogens and iron. Non-limiting examples of bridging group Amay be represented by R′₂C, R′₂Si, R′₂Si R′₂Si, R′₂Ge, R′P, where R′ isindependently, a radical group which is hydride, hydrocarbyl,substituted hydrocarbyl, halocarbyl, substituted halocarbyl,hydrocarbyl-substituted organometalloid, halocarbyl-substitutedorganometalloid, disubstituted boron, disubstituted pnictogen,substituted chalcogen, or halogen or two or more R′ may be joined toform a ring or ring system. In one embodiment, the bridged, bulky ligandmetallocene-type catalyst compounds of formula (IV) have two or morebridging groups A (EP 664 301 B1).

In one embodiment, the bulky ligand metallocene-type catalyst compoundsare those where the R substituents on the bulky ligands L^(A) and L^(B)of formulas (III) and (IV) are substituted with the same or differentnumber of substituents on each of the bulky ligands. In anotherembodiment, the bulky ligands L^(A) and L^(B) of formulas (III) and (IV)are different from each other.

Other bulky ligand metallocene-type catalyst compounds and catalystsystems useful in the invention may include those described in U.S. Pat.Nos. 5,064,802, 5,145,819, 5,149,819, 5,243,001, 5,239,022, 5,276,208,5,296,434, 5,321,106, 5,329,031, 5,304,614, 5,677,401, 5,723,398,5,753,578, 5,854,363, 5,856,543, 5,858,903, 5,859,158, 5,900,517 and5,939,503 and PCT publications WO 93/08221, WO 93/08199, WO 95/07140, WO98/11144, WO 98/41530, WO 98/41529, WO 98/46650, WO 99/02540 and WO99/14221 and European publications EP-A-0 578 838, EP-A-0 638 595,EP-B-0 513 380, EP-A1-0 816 372, EP-A2-0 839 834, EP-B1-0 632 819,EP-B1-0 748 821 and EP-B1-0 757 996, all of which are herein fullyincorporated by reference.

In one embodiment, bulky ligand metallocene-type catalysts compoundsuseful in the invention include bridged heteroatom, mono-bulky ligandmetallocene-type compounds. These types of catalysts and catalystsystems are described in, for example, PCT publication WO 92/00333, WO94/07928, WO 91/04257, WO 94/03506, WO 96/00244, WO 97/15602 and WO99/20637 and U.S. Pat. Nos. 5,057,475, 5,096,867, 5,055,438, 5,198,401,5,227,440 and 5,264,405 and European publication EP-A-0 420 436, all ofwhich are herein fully incorporated by reference.

In this embodiment, the bulky ligand metallocene-type catalyst compoundis represented by the formula:

L^(C)AJMQ_(n)  (V)

where M is a Group 3 to 16 metal atom or a metal selected from the Groupof actinides and lanthanides of the Periodic Table of Elements,preferably M is a Group 4 to 12 transition metal, and more preferably Mis a Group 4, 5 or 6 transition metal, and most preferably M is a Group4 transition metal in any oxidation state, especially titanium; L^(C) isa substituted or unsubstituted bulky ligand bonded to M; J is bonded toM; A is bonded to M and J; J is a heteroatom ancillary ligand; and A isa bridging group; Q is a univalent anionic ligand; and n is the integer0, 1 or 2. In formula (V) above, L^(C), A and J form a fused ringsystem. In an embodiment, L^(C) of formula (V) is as defined above forL^(A), A, M and Q of formula (V) are as defined above in formula (III).

In formula (V), J is a heteroatom containing ligand in which J is anelement with a coordination number of three from Group 15 or an elementwith a coordination number of two from Group 16 of the Periodic Table ofElements. Preferably J contains a nitrogen, phosphorus, oxygen or sulfuratom with nitrogen being most preferred.

In an embodiment of the invention, the bulky ligand metallocene-typecatalyst compounds are heterocyclic ligand complexes where the bulkyligands, the ring(s) or ring system(s), include one or more heteroatomsor a combination thereof. Non-limiting examples of heteroatoms include aGroup 13 to 16 element, preferably nitrogen, boron, sulfur, oxygen,aluminum, silicon, phosphorous and tin. Examples of these bulky ligandmetallocene-type catalyst compounds are described in WO 96/33202, WO96/34021, WO 97/17379 and WO 98/22486 and EP-A1-0 874 005 and U.S. Pat.No. 5,637,660, 5,539,124, 5,554,775, 5,756,611, 5,233,049, 5,744,417,and 5,856,258 all of which are herein incorporated by reference.

In one embodiment, the bulky ligand metallocene-type catalyst compoundsare those complexes known as transition metal catalysts based onbidentate ligands containing pyridine or quinoline moieties, such asthose described in U.S. application Ser. No. 09/103,620 filed Jun. 23,1998, which is herein incorporated by reference. In another embodiment,the bulky ligand metallocene-type catalyst compounds are those describedin PCT publications WO 99/01481 and WO 98/42664, which are fullyincorporated herein by reference.

In a preferred embodiment, the bulky ligand type metallocene-typecatalyst compound is a complex of a metal, preferably a transitionmetal, a bulky ligand, preferably a substituted or unsubstitutedpi-bonded ligand, and one or more heteroallyl moieties, such as thosedescribed in U.S. Pat. Nos. 5,527,752 and 5,747,406 and EP-B1-0 735 057,all of which are herein fully incorporated by reference.

In a particularly preferred embodiment, the other metal compound orsecond metal compound is the bulky ligand metallocene-type catalystcompound is represented by the formula:

L^(D)MQ₂(YZ)X_(n)  (VI)

where M is a Group 3 to 16 metal, preferably a Group 4 to 12 transitionmetal, and most preferably a Group 4, 5 or 6 transition metal; L^(D) isa bulky ligand that is bonded to M; each Q is independently bonded to Mand Q₂(YZ) forms a ligand, preferably a unicharged polydentate ligand; Aor Q is a univalent anionic ligand also bonded to M; X is a univalentanionic group when n is 2 or X is a divalent anionic group when n is 1;n is 1 or 2.

In formula (VI), L and M are as defined above for formula (III). Q is asdefined above for formula (III), preferably Q is selected from the groupconsisting of —O—, —NR—, —CR₂— and —S—; Y is either C or S; Z isselected from the group consisting of —OR, —NR₂, —CR₃, —SR, —SiR₃, —PR₂,—H, and substituted or unsubstituted aryl groups, with the proviso thatwhen Q is —NR— then Z is selected from one of the group consisting of—OR, —NR₂, —SR, —SiR₃, —PR₂ and —H; R is selected from a groupcontaining carbon, silicon, nitrogen, oxygen, and/or phosphorus,preferably where R is a hydrocarbon group containing from 1 to 20 carbonatoms, most preferably an alkyl, cycloalkyl, or an aryl group; n is aninteger from 1 to 4, preferably 1 or 2; X is a univalent anionic groupwhen n is 2 or X is a divalent anionic group when n is 1; preferably Xis a carbamate, carboxylate, or other heteroallyl moiety described bythe Q, Y and Z combination.

In a particularly preferred embodiment the bulky ligand metallocene-typecompound is represented by the formula:

Phenoxide Catalysts

Another group of catalysts that may be used in the process of thisinvention include one or more catalysts represented by the followingformulae:

wherein R¹ is hydrogen or a C₄ to C₁₀₀ group, preferably a tertiaryalkyl group, preferably a C₄ to C₂₀ alkyl group, preferably a C₄ to C₂₀tertiary alkyl group, preferably a neutral C₄ to C₁₀₀ group and may ormay not also be bound to M, and at least one of R² to R⁵ is a groupcontaining a heteroatom, the rest of R² to R⁵ are independently hydrogenor a C₁ to C₁₀₀ group, preferably a C₄ to C₂₀ alkyl group (preferablybutyl, isobutyl, pentyl hexyl, heptyl, isohexyl, octyl, isooctyl, decyl,nonyl, dodecyl ) and any of R² to R⁵ also may or may not be bound to M,O is oxygen, M is a group 3 to group 10 transition metal or lanthanidemetal, preferably a group 4 metal, preferably Ti, Zr or Hf, n is thevalence state of the metal M, preferably 2, 3, 4, or 5, Q is an alkyl,halogen, benzyl, amide, carboxylate, carbamate, thiolate, hydride oralkoxide group, or a bond to an R group containing a heteroatom whichmay be any of R¹ to R⁵ A heteroatom containing group may be anyheteroatom or a heteroatom bound to carbon silica or another heteroatom.Preferred heteroatoms include boron, aluminum, silicon, nitrogen,phosphorus, arsenic, tin, lead, antimony, oxygen, selenium, tellurium.Particularly preferred heteroatoms include nitrogen, oxygen, phosphorus,and sulfur. Even more particularly preferred heteroatoms include oxygenand nitrogen. The heteroatom itself may be directly bound to thephenoxide ring or it may be bound to another atom or atoms that arebound to the phenoxide ring. The heteroatom containing group may containone or more of the same or different heteroatoms. Preferred heteroatomgroups include imines, amines, oxides, phosphines, ethers, ketenes,oxoazolines heterocyclics, oxazolines, thioethers, and the like.Particularly preferred heteroatom groups include imines. Any twoadjacent R groups may form a ring structure, preferably a 5 or 6membered ring. Likewise the R groups may form multi-ring structures. Inone embodiment any two or more R groups do not form a 5 membered ring.

These phenoxide catalysts may be activated with activators includingalkyl aluminum compounds (such as diethylaluminum chloride), alumoxanes,modified alumoxanes, non-coordinating anions, non-coordinating group 13metal or metalliod anions, boranes, borates and the like. For furtherinformation on activators please see the ACTIVATOR section below.

Conventional-Type Transition Metal Catalysts

Conventional-type transition metal catalysts are those traditionalZiegler-Natta, vanadium and Phillips-type catalysts well known in theart. Such as, for example Ziegler-Natta catalysts as described inZiegler-Natta Catalysts and Polymerizations, John Boor, Academic Press,New York, 1979. Examples of conventional-type transition metal catalystsare also discussed in U.S. Pat. Nos. 4,115,639, 4,077,904, 4,482,687,4,564,605, 4,721,763, 4,879,359 and 4,960,741 all of which are hereinfully incorporated by reference. The conventional-type transition metalcatalyst compounds that may be used in the present invention includetransition metal compounds from Groups 3 to 17, preferably 4 to 12, morepreferably 4 to 6 of the Periodic Table of Elements.

These conventional-type transition metal catalysts may be represented bythe formula: MR_(x), where M is a metal from Groups 3 to 17, preferablyGroup 4 to 6, more preferably Group 4, most preferably titanium; R is ahalogen or a hydrocarbyloxy group; and x is the oxidation state of themetal M. Non-limiting examples of R include alkoxy, phenoxy, bromide,chloride and fluoride. Non-limiting examples of conventional-typetransition metal catalysts where M is titanium include TiCl₄, TiBr₄,Ti(OC₂H₅)₃Cl, Ti(OC₂H₅)Cl₃, Ti(OC₄H₉)₃Cl, Ti(OC₃H₇)₂Cl₂, Ti(OC₂H₅)₂Br₂,TiCl₃.1/3AlCl₃ and Ti(OC₁₂H₂₅)Cl₃.

Conventional-type transition metal catalyst compounds based onmagnesium/titanium electron-donor complexes that are useful in theinvention are described in, for example, U.S. Pat. Nos. 4,302,565 and4,302,566, which are herein fully incorporate by reference. The MgTiCl₆(ethyl acetate)₄ derivative is particularly preferred.

British Patent Application 2,105,355 and U.S. Pat. No. 5,317,036, hereinincorporated by reference, describes various conventional-type vanadiumcatalyst compounds. Non-limiting examples of conventional-type vanadiumcatalyst compounds include vanadyl trihalide, alkoxy halides andalkoxides such as VOCl₃, VOCl₂(OBu) where Bu=butyl and VO(OC₂H₅)₃;vanadium tetra-halide and vanadium alkoxy halides such as VCl₄ andVCl₃(OBu); vanadium and vanadyl acetyl acetonates and chloroacetylacetonates such as V(AcAc)₃ and VOCl₂(AcAc) where (AcAc) is an acetylacetonate. The preferred conventional-type vanadium catalyst compoundsare VOCl₃, VCl₄ and VOCl₂—OR where R is a hydrocarbon radical,preferably a C₁ to C₁₀ aliphatic or aromatic hydrocarbon radical such asethyl, phenyl, isopropyl, butyl, propyl, n-butyl, iso-butyl,tertiary-butyl, hexyl, cyclohexyl, naphthyl, etc., and vanadium acetylacetonates.

Conventional-type chromium catalyst compounds, often referred to asPhillips-type catalysts, suitable for use in the present inventioninclude CrO₃, chromocene, silyl chromate, chromyl chloride (CrO₂Cl₂),chromium-2-ethyl-hexanoate, chromium acetylacetonate (Cr(AcAc)₃), andthe like. Non-limiting examples are disclosed in U.S. Pat. Nos.3,709,853, 3,709,954, 3,231,550, 3,242,099 and 4,077,904, which areherein fully incorporated by reference.

Still other conventional-type transition metal catalyst compounds andcatalyst systems suitable for use in the present invention are disclosedin U.S. Pat. Nos. 4,124,532, 4,302,565, 4,302,566, 4,376,062, 4,379,758,5,066,737, 5,763,723, 5,849,655, 5,852,144, 5,854,164 and 5,869,585 andpublished EP-A2 0 416 815 A2 and EP-A1 0 420 436, which are all hereinincorporated by reference.

Other catalysts may include cationic catalysts such as AlCl₃, and othercobalt, iron, nickel and palladium catalysts well known in the art. Seefor example U.S. Pat. Nos. 3,487,112, 4,472,559, 4,182,814 and 4,689,437all of which are incorporated herein by reference.

Typically, these conventional-type transition metal catalyst compoundsexcluding some conventional-type chromium catalyst compounds areactivated with one or more of the conventional-type cocatalystsdescribed below.

Conventional-Type Cocatalysts

Conventional-type cocatalyst compounds for the above conventional-typetransition metal catalyst compounds may be represented by the formulaM³M⁴ _(v)X² _(c)R³ _(b-e), wherein M³ is a metal from Group 1 to 3 and12 to 13 of the Periodic Table of Elements; M⁴ is a metal of Group 1 ofthe Periodic Table of Elements; v is a number from 0 to 1; each X² isany halogen; c is a number from 0 to 3; each R³ is a monovalenthydrocarbon radical or hydrogen; b is a number from 1 to 4; and whereinb minus c is at least 1. Other conventional-type organometalliccocatalyst compounds for the above conventional-type transition metalcatalysts have the formula M³R³ _(k), where M³ is a Group IA, II, IIB orIIIA metal, such as lithium, sodium, beryllium, barium, boron, aluminum,zinc, cadmium, and gallium; k equals 1, 2 or 3 depending upon thevalency of M³ which valency in turn normally depends upon the particularGroup to which M³ belongs; and each R³ may be any monovalent hydrocarbonradical.

Non-limiting examples of conventional-type organometallic cocatalystcompounds useful with the conventional-type catalyst compounds describedabove include methyllithium, butyllithium, dihexylmercury,butylmagnesium, diethylcadmium, benzylpotassium, diethylzinc,tri-n-butylaluminum, diisobutyl ethylboron, diethylcadmium,di-n-butylzinc and tri-n-amylboron, and, in particular, the aluminumalkyls, such as tri-hexyl-aluminum, triethylaluminum, trimethylaluminum,and tri-isobutylaluminum. Other conventional-type cocatalyst compoundsinclude mono-organohalides and hydrides of Group 2 metals, and mono- ordi-organohalides and hydrides of Group 3 and 13 metals. Non-limitingexamples of such conventional-type cocatalyst compounds includedi-isobutylaluminum bromide, isobutylboron dichloride, methyl magnesiumchloride, ethylberyllium chloride, ethylcalcium bromide,di-isobutylaluminum hydride, methylcadmium hydride, diethylboronhydride, hexylberyllium hydride, dipropylboron hydride, octylmagnesiumhydride, butylzinc hydride, dichloroboron hydride, di-bromoaluminumhydride and bromocadmium hydride. Conventional-type organometalliccocatalyst compounds are known to those in the art and a more completediscussion of these compounds may be found in U.S. Pat. Nos. 3,221,002and 5,093,415, which are herein fully incorporated by reference.

Activators

The catalysts, preferably the group 15 metal compoundand/or themetallocene cataysts described herein, are preferably combined with oneor more activators to form olefin polymerization catalyst systems.Preferred activators include alkyl aluminum compounds (such asdiethylaluminum chloride), alumoxanes, modified alumoxanes,non-coordinating anions, non-coordinating group 13 metal or metalliodanions, boranes, borates and the like. It is within the scope of thisinvention to use alumoxane or modified alumoxane as an activator, and/orto also use ionizing activators, neutral or ionic, such as tri (n-butyl)ammonium tetrakis (pentafluorophenyl) boron or a trisperfluorophenylboron metalloid precursor which ionize the neutral metallocene compound.Other useful compounds include triphenyl boron, triethyl boron,tri-n-butyl ammonium tetraethylborate, triaryl borane and the like.Other useful compounds include aluminate salts as well.

In a preferred embodiment modified alumoxanes are combined with thecatalysts to form a catalyst system. In a preferred embodiment MMAO3A(modified methyl alumoxane in heptane, commercially available from AkzoChemicals, Inc. under the trade name Modified Methylalumoxane type 3A,covered under patent number U.S. Pat. No. 5,041,584) is combined withthe first and second metal compounds to form a catalyst system.

There are a variety of methods for preparing alumoxane and modifiedalumoxanes, non-limiting examples of which are described in U.S. Pat.No. 4,665,208, 4,952,540, 5,091,352, 5,206,199, 5,204,419, 4,874,734,4,924,018, 4,908,463, 4,968,827, 5,308,815, 5,329,032, 5,248,801,5,235,081, 5,157,137, 5,103,031, 5,391,793, 5,391,529, 5,041,5845,693,838, 5,731,253, 5,041,584 and 5,731,451 and European publicationsEP-A-0 561 476, EP-B1-0 279 586 and EP-A-0 594-218, and PCT publicationWO 94/10180, all of which are herein fully incorporated by reference.

Ionizing compounds may contain an active proton, or some other cationassociated with but not coordinated to or only loosely coordinated tothe remaining ion of the ionizing compound. Such compounds and the likeare described in European publications EP-A-0 570 982, EP-A-0 520 732,EP-A-0 495 375, EP-A-0 426 637, EP-A-500 944, EP-A-0 277 003 and EP-A-0277 004, and U.S. Pat. Nos. 5,153,157, 5,198,401, 5,066,741, 5,206,197,5,241,025, 5,387,568, 5,384,299, 5,502,124 and 5,643,847, all of whichare herein fully incorporated by reference. Other activators includethose described in PCT publication WO 98/07515 such as tris(2,2′,2″-nonafluorobiphenyl) fluoroaluminate, which is fullyincorporated herein by reference. Combinations of activators are alsocontemplated by the invention, for example, alumoxanes and ionizingactivators in combinations, see for example, PCT publications WO94/07928 and WO 95/14044 and U.S. Pat. Nos. 5,153,157 and 5,453,410 allof which are herein fully incorporated by reference. Also, methods ofactivation such as using radiation and the like are also contemplated asactivators for the purposes of this invention.

When two different catalysts are used, the first and second catalystcompounds may be combined at molar ratios of 1:1000 to 1000:1,preferably 1:99 to 99:1, preferably 10:90 to 90:10, more preferably20:80 to 80:20, more preferably 30:70 to 70:30, more preferably 40:60 to60:40. The particular ratio chosen will depend on the end productdesired and/or the method of activation. One practical method todetermine which ratio is best to obtain the desired polymer is to startwith a 1:1 ratio, measure the desired property in the product producedand adjust the ratio accordingly.

In one particular embodiment, when using Compound I and indenylzirconium tris-pivalate where both are activated with the sameactivator, the preferred weight percents, based upon the weight of thetwo catalysts, but not the activator or any support, are 10 to 95 weight% Compound I and 5 to 90 weight % indenyl zirconium tris-pivalate,preferably 50 to 90 weight % Compound I and 40 to 50 weight % indenylzirconium tris-pivalate, more preferably 60-80 weight % Compound I to 40to 20 weight % indenyl zirconium tris-pivalate. In a particularlypreferred embodiment the indenyl zirconium tris-pivalate is activatedwith methylalumoxane, then combined with Compound I, then injected inthe reactor.

Multi-component catalyst systems with similar activity decay ratesprovide a route for olefin polymerization in which the effects ofcatalyst residence time in the reactor can be mitigated. The catalystspreferably have a decay rate that is similar as measured by a decaymodel, be it first or higher order. The decay rates or alternatively,the catalyst half lives, are preferably within about 40% of each other,more preferably about 20% of each other, and most preferably about 10 to0% of each other. 0% would mean essentially the same.

It is recognized that the decay characteristics can be affected bytemperature, monomer pressure, comonomer type and concentration,hydrogen, additives/modifiers/other catalysts, catalyst poisons orimpurities in the gas stream, presence of condensing agents or operationin condensing-mode.

A corollary to this is that one or both of the catalysts can have a fastdecay such that they are relatively insensitive to residence timeeffects in the normal range of reactor operation. One can calculate howmuch the decay rates can differ between catalysts based upon theirrespective decay rates, in order that the variation of polymerproperties in the reactor is relatively small when there are changes inresidence time.

In another embodiment the first catalyst is selected because when usedalone it produces a high weight average molecular weight polymer (suchas for example above 100,000, preferably above 150,000, preferably above200,000, preferably above 250,000, more preferably above 300,000) andthe second catalyst is selected because when used alone it produces alow molecular weight polymer (such as for example below 80,000,preferably below 70,000, preferably below 60,000, more preferably below50,000, more preferably below 40,000, more preferably below 30,000, morepreferably below 20,000 and above 5,000, more preferably below 20,000and above 10,000).

When two or more catalysts are used, multi-component catalystpolymerization split can be estimated and controlled by perturbing thefeed rate of one or both of the catalyst feed rates to thepolymerization reactor and measuring the change in polymer productionrate. The invention is especially useful when the catalysts areindistinguishable elementally but can be used with other systems. It isespecially applicable in systems where the relative amounts of eachcatalyst can be easily varied such as for solution feed or hybridsolution feed.

The change in catalyst feed is less than 40%, preferably less than 15%and most preferably about 5 to 10%. There are accompanying changes inthe polymer split composition, however, these are relatively small andmay be inconsequential as the timeframe for observing changes inproduction rate may be short relative to residence time in the reactor.The change in polymer composition is diluted.

The production rate need not line out, but can be estimatedmathematically when it is about 30 to 80% of its final value based upontheoretical response of CSTR (continuous stirred tank reactor) to a stepchange.

The simplest case is for a catalyst with very fast decay so residencetime effects are inconsequential (although decay can easily be dealtwith using a simple formula). As an example, let catalyst A and B be fedat a 50:50 rate, producing 10,000 pph of resin. Increase catalyst A by10% and hold B constant so the feed split is now 55:50. The productionrate increases from 10,000 to 10,500 pph. The difference of 5000 pph isattributable to the 10% increase of catalyst A, so the initial amount ofresin produce by A was 5000 pph and its new value is 5500 pph. Theinitial polymer split was 50:50 and the new split is 55:50. (In thisexample, the catalysts were taken to be equally active, but theequations work for other systems.)

The catalyst feed rate of one or both catalysts can be constantlyperturbed by small amounts continuously around the aim split (back andforth) so that the net resin composition is always aim. A step change ismade and the response measured. The system performance can include anupdate term based on measured split to account for variations incatalyst productivity and decay.

Catalyst productivity models including the effects of temperature,residence time, monomer partial pressure, comonomer type andconcentration, hydrogen concentration, impurities, inerts such asisopentane, and/or operation in or close to condensing mode can be usedfor each component of a separate addition, multi-componentpolymerization system for polymerization fraction split control. Inresponse to changes in variables, the feed rates of component catalystscan be adjusted. For example, a change in residence time can becompensated for by forward control that automatically adjusts thecatalysts feed rates to a new aim value. Effects of temperature, partialpressure and other variables can also be compensated in a feed forwardfashion.

The models can also be used for process control based upon measuredpolymer split fractions. Ethylene partial pressure, for example could beadjusted by the models based upon the measured split. The concentrationof an inert that affects the productivity of one catalyst more than theother could also be adjusted (like isopentane due presumably to itstempered cooling effect).

Most commonly, the catalyst feed rates would be adjusted to move themeasured polymer split back to aim. The effects of catalyst decay andresidence time are part of the model, so the even the use of catalystswith significant or different decay rates can be controlled.

The instant invention is applicable to gas phase polymerization withsolution or liquid feed.

In general the combined catalysts and the activator are combined inratios of about 1000:1 to about 0.5:1. In a preferred embodiment thecatalysts and the activator are combined in a ratio of about 300:1 toabout 1:1, preferably about 150:1 to about 1:1, for boranes, borates,aluminates, etc. the ratio is preferably about 1:1 to about 10:1 and foralkyl aluminum compounds (such as diethylaluminum chloride combined withwater) the ratio is preferably about 0.5:1 to about 10:1.

Polymerization Process

The catalysts, activators and catalyst systems described above aresuitable for use in any polymerization process, including solution, gasor slurry processes or a combination thereof, most preferably a gas orslurry phase process.

In one embodiment, this invention is directed toward the polymerizationor copolymerization reactions involving the polymerization of one ormore monomers having from 2 to 30 carbon atoms, preferably 2-12 carbonatoms, and more preferably 2 to 8 carbon atoms. The invention isparticularly well suited to the copolymerization reactions involving thepolymerization of one or more olefin monomers of ethylene, propylene,butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1, decene-1,3-methyl-pentene-1, 3,5,5-trimethyl-hexene-1 and cyclic olefins or acombination thereof. Other monomers can include vinyl monomers,diolefins such as dienes, polyenes, norbornene, norbornadiene monomers.Preferably a copolymer of ethylene is produced, where the comonomer isat least one alpha-olefin having from 4 to 15 carbon atoms, preferablyfrom 4 to 12 carbon atoms, more preferably from 4 to 8 carbon atoms andmost preferably from 4 to 7 carbon atoms. In an alternate embodiment,the geminally disubstituted olefins disclosed in WO 98/37109 may bepolymerized or copolymerized using the invention herein described.

In another embodiment ethylene or propylene is polymerized with at leasttwo different comonomers to form a terpolymer. The preferred comonomersare a combination of alpha-olefin monomers having 4 to 10 carbon atoms,more preferably 4 to 8 carbon atoms, optionally with at least one dienemonomer. The preferred terpolymers include the combinations such asethylene/butene-1/hexene-1, ethylene/propylene/butene-1,propylene/ethylene/hexene-1, ethylene/propylene/ norbornene and thelike.

In a particularly preferred embodiment the process of the inventionrelates to the polymerization of ethylene and at least one comonomerhaving from 4 to 8 carbon atoms, preferably 4 to 7 carbon atoms.Particularly, the comonomers are butene-1, 4-methyl-pentene-1, hexene-1and octene-1, the most preferred being hexene-1 and/or butene-1.

Typically in a gas phase polymerization process a continuous cycle isemployed where in one part of the cycle of a reactor system, a cyclinggas stream, otherwise known as a recycle stream or fluidizing medium, isheated in the reactor by the heat of polymerization. This heat isremoved from the recycle composition in another part of the cycle by acooling system external to the reactor. Generally, in a gas fluidizedbed process for producing polymers, a gaseous stream containing one ormore monomers is continuously cycled through a fluidized bed in thepresence of a catalyst under reactive conditions. The gaseous stream iswithdrawn from the fluidized bed and recycled back into the reactor.Simultaneously, polymer product is withdrawn from the reactor and freshmonomer is added to replace the polymerized monomer. (See for exampleU.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036, 5,352,749,5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661 and 5,668,228 allof which are fully incorporated herein by reference.)

The reactor pressure in a gas phase process may vary from about 10 psig(69 kPa) to about 500 psig (3448 kPa), preferably in the range of fromabout 100 psig (690 kPa) to about 400 psig (2759 kPa), preferably in therange of from about 200 psig (1379 kPa) to about 400 psig (2759 kPa),more preferably in the range of from about 250 psig (1724 kPa) to about350 psig (2414 kPa).

The reactor temperature in the gas phase process may vary from about 30°C. to about 120° C., preferably from about 60° C. to about 115° C., morepreferably in the range of from about 75° C. to 110° C., and mostpreferably in the range of from about 85° C. to about 110° C. Alteringthe polymerization temperature can also be used as a tool to alter thefinal polymer product properties.

The productivity of the catalyst(s) or catalyst system(s) is influencedby the main monomer partial pressure. The preferred mole percent of themain monomer, ethylene or propylene, preferably ethylene, is from about25 to 90 mole percent and the monomer partial pressure is in the rangeof from about 75 psia (517 kPa) to about 300 psia (2069 kPa), which aretypical conditions in a gas phase polymerization process. In oneembodiment the ethylene partial pressure is about 220 to 240 psi(1517-1653 kPa). In another embodiment the molar ratio of hexene toethylene ins the reactor is 0.03:1 to 0.08:1.

In a preferred embodiment, the reactor utilized in the present inventionand the process of the invention produce greater than 500 lbs of polymerper hour (227 Kg/hr) to about 200,000 lbs/hr (90,900 Kg/hr) or higher ofpolymer, preferably greater than 1000 lbs/hr (455 Kg/hr), morepreferably greater than 10,000 lbs/hr (4540 Kg/hr), even more preferablygreater than 25,000 lbs/hr (11,300 Kg/hr), still more preferably greaterthan 35,000 lbs/hr (15,900 Kg/hr), still even more preferably greaterthan 50,000 lbs/hr (22,700 Kg/hr) and most preferably greater than65,000 lbs/hr (29,000 Kg/hr) to greater than 100,000 lbs/hr (45,500Kg/hr).

Other gas phase processes contemplated by the process of the inventioninclude those described in U.S. Pat. Nos. 5,627,242, 5,665,818 and5,677,375, and European publications EP-A-0 794 200, EP-A-0 802 202 andEP-B-634 421 all of which are herein fully incorporated by reference.

A slurry polymerization process generally uses pressures in the range offrom about 1 to about 50 atmospheres and even greater and temperaturesin the range of 0° C. to about 120° C. In a slurry polymerization, asuspension of solid, particulate polymer is formed in a liquidpolymerization diluent medium to which ethylene and comonomers and oftenhydrogen along with catalyst are added. The suspension including diluentis intermittently or continuously removed from the reactor where thevolatile components are separated from the polymer and recycled,optionally after a distillation, to the reactor. The liquid diluentemployed in the polymerization medium is typically an alkane having from3 to 7 carbon atoms, preferably a branched alkane. The medium employedshould be liquid under the conditions of polymerization and relativelyinert. When a propane medium is used the process must be operated abovethe reaction diluent critical temperature and pressure. Preferably, ahexane or an isobutane medium is employed.

In one embodiment, a preferred polymerization technique of the inventionis referred to as a particle form polymerization, or a slurry processwhere the temperature is kept below the temperature at which the polymergoes into solution. Such technique is well known in the art, anddescribed in for instance U.S. Pat. No. 3,248,179 which is fullyincorporated herein by reference. The preferred temperature in theparticle form process is within the range of about 185° F. (85° C.) toabout 230° F. (110° C.). Two preferred polymerization methods for theslurry process are those employing a loop reactor and those utilizing aplurality of stirred reactors in series, parallel, or combinationsthereof. Non-limiting examples of slurry processes include continuousloop or stirred tank processes. Also, other examples of slurry processesare described in U.S. Pat. No. 4,613,484, which is herein fullyincorporated by reference.

In another embodiment, the slurry process is carried out continuously ina loop reactor. The catalyst(s) and/or activator(s) as a solution, as asuspension, as an emulsion, or as a slurry in isobutane or as a dry freeflowing powder is injected regularly to the reactor loop, which isitself filled with circulating slurry of growing polymer particles in adiluent of isobutane containing monomer and comonomer. Hydrogen,optionally, may be added as a molecular weight control. The reactor ismaintained at pressure of about 525 psig to 625 psig (3620 kPa to 4309kPa) and at a temperature in the range of about 140° F. to about 220° F.(about 60° C. to about 104° C.) depending on the desired polymerdensity. Reaction heat is removed through the loop wall since much ofthe reactor is in the form of a double-jacketed pipe. The slurry isallowed to exit the reactor at regular intervals or continuously to aheated low pressure flash vessel, rotary dryer and a nitrogen purgecolumn in sequence for removal of the isobutane diluent and allunreacted monomer and comonomers. The resulting hydrocarbon free powderis then compounded for use in various applications.

In an embodiment the reactor used in the slurry process of the inventionis capable of and the process of the invention is producing greater than2000 lbs of polymer per hour (907 Kg/hr), more preferably greater than5000 lbs/hr (2268 Kg/hr), and most preferably greater than 10,000 lbs/hr(4540 Kg/hr). In another embodiment the slurry reactor used in theprocess of the invention is producing greater than 15,000 lbs of polymerper hour (6804 Kg/hr), preferably greater than 25,000 lbs/hr (11,340Kg/hr) to about 100,000 lbs/hr (45,500 Kg/hr).

In another embodiment in the slurry process of the invention the totalreactor pressure is in the range of from 400 psig (2758 kPa) to 800 psig(5516 kPa), preferably 450 psig (3103 kPa) to about 700 psig (4827 kPa),more preferably 500 psig (3448 kPa) to about 650 psig (4482 kPa), mostpreferably from about 525 psig (3620 kPa) to 625 psig (4309 kPa).

In yet another embodiment in the slurry process of the invention theconcentration of ethylene in the reactor liquid medium is in the rangeof from about 1 to 10 weight percent, preferably from about 2 to about 7weight percent, more preferably from about 2.5 to about 6 weightpercent, most preferably from about 3 to about 6 weight percent.

A preferred process of the invention is where the process, preferably aslurry or gas phase process is operated in the absence of or essentiallyfree of any scavengers, such as triethylaluminum, trimethylaluminum,tri-isobutylaluminum and tri-n-hexylaluminum and diethyl aluminumchloride, dibutyl zinc and the like. This preferred process is describedin PCT publication WO 96/08520 and U.S. Pat. No. 5,712,352, which areherein fully incorporated by reference.

In another preferred embodiment the one or all of the catalysts arecombined with up to 10 weight % of a metal stearate, (preferably aaluminum stearate, more preferably aluminum distearate) based upon theweight of the catalyst system (or its components), any support and thestearate. In an alternate embodiment a solution of the metal stearate isfed into the reactor. In another embodiment the metal stearate is mixedwith the catalyst and fed into the reactor separately. These agents maybe mixed with the catalyst or may be fed into the reactor in a solutionor a slurry with or without the catalyst system or its components.

In another preferred embodiment the supported catalysts combined withthe activators are tumbled with 1 weight % of aluminum distearate or 2weight % of an antistat, such as a methoxylated amine, such as Witco'sKemamine AS-990 from ICI Specialties in Bloomington Del. In anotherembodiment, a supported catalyst system of component is combined with 2to 3 weight % of a metal stearate, based upon the weight of the catalystsystem (or its components), any support and the stearate.

More information on using aluminum stearate type additives may be foundin U.S. Pat. Ser. No. 09/113,261 filed Jul. 10, 1998, which isincorporated by reference herein.

In a preferred embodiment a slurry of the stearate in mineral oil isintroduced into the reactor separately from the metal compounds and orthe activators.

Experience with solution catalyst has shown that a smooth MMAO flow rateis better for maintaining a low static level in the reactor. Also, quickchanges in MMAO flow, either up or down, are preferably avoided or elseextreme static levels could be generated.

Reduced static levels will result in reduced agglomeration and sheetingepisodes.

While solution or slurry is a referenced embodiment, the catalyst and/orthe activator may be placed on, deposited on, contacted with,incorporated within, adsorbed, or absorbed in a support. Typically thesupport can be of any of the solid, porous supports, includingmicroporous supports. Typical support materials include talc; inorganicoxides such as silica, magnesium chloride, alumina, silica-alumina;polymeric supports such as polyethylene, polypropylene, polystyrene,cross-linked polystyrene; and the like. Preferably the support is usedin finely divided form. Prior to use the support is preferably partiallyor completely dehydrated. The dehydration may be done physically bycalcining or by chemically converting all or part of the activehydroxyls. For more information on how to support catalysts please seeU.S. Pat. No. 4,808,561 which discloses how to support a metallocenecatalyst system. The techniques used therein are generally applicablefor this invention.

In another embodiment NMR (or other) equipment is used to analyze thefeed stream composition of the catalyst solution prior to injecting itinto a polymerization reactor. The information is then used to controlindividual feed streams and thus the final polymer product.

In another embodiment a selective poison is added to the polymerizationwhich selectively deactivates one of the catalysts in a controlledmanner and thereby controls the active split of polymer being produced.Preferred selective poisons include carbon dioxide, carbon monoxide,various internal olefins and dienes, oxygen, Lewis bases such as ethers,esters, and various amines.

In another embodiment if catalyst from one feeder is lost or interruptedduring the independent (but mixed) addition of two or more catalyst to apolymerization, the other catalyst feeder(s) are stopped within about 30minutes, preferably within about 5 minutes, most preferably within about2 minutes or immediately. The reactor may be killed or mini-killed ifresidence effects are expected to drive the split off specification whenthe reactor is operating with no fresh catalyst feed and catalyst feedcannot be restored within a specific period of time dependent upon theperformance of the catalysts.

Invention should be applicable to gas phase polymerization with solutionfeed or hybrid solution feed system.

In a preferred embodiment, the polymer produced herein has an I₂₁ (asmeasured by ASTM 1238, condition E, at 190° C.) of 20 g/10 min or less,preferably 15 g/10 min or less, preferably 12 or less, more preferablybetween 5 and 10 g/10 min, more preferably between 6 and 8 g/10 min anda melt flow index “MIR” of I₂₁/I₂ (as measured by ASTM 1238, condition Eand F, at 190° C.) of 80 or more, preferably 90 or more, preferably 100or more, preferably 125 or more.

In another embodiment, the polymer has an I₂₁ (as measured by ASTM 1238,condition E, at 190° C.) of 20 g/10 min or less, preferably 15 g/10 minor less, preferably 12 or less, more preferably between 5 and 10 g/10min, more preferably between 6 and 8 g/10 min and a melt flow index“MIR” of I₂₁/I₂ (as measured by ASTM 1238, condition E, at 190° C.) of80 or more, preferably 90 or more, preferably 100 or more, preferably125 or more and has one or more of the following properties in addition:

(a) Mw/Mn of between 15 and 80, preferably between 20 and 60, preferablybetween 20 and 40;

(b) an Mw of 180,000 or more, preferably 200,000 or more, preferably250,000 or more, preferably 300,000 or more;

(c) a density (as measured by ASTM 2839) of 0.94 to 0.970 g/cm³;preferably 0.945 to 0.965 g/cm³; preferably 0.950 to 0.960 g/cm³;

(e) a residual metal content of 2.0 ppm transition metal or less,preferably 1.8 ppm transition metal or less, preferably 1.6 ppmtransition metal or less, preferably 1.5 ppm transition metal or less,preferably 2.0 ppm or less of group 4 metal, preferably 1.8 ppm or lessof group 4 metal, preferably 1.6 ppm or less of group 4 metal,preferably 1.5 ppm or less of group 4 metal, preferably 2.0 ppm or lesszirconium, preferably 1.8 ppm or less zirconium, preferably 1.6 ppm orless zirconium, preferably 1.5 ppm or less zirconium(as measured byInductively Coupled Plasma Optical Emission Spectroscopy run againstcommercially available standards, where the sample is heated so as tofully decompose all organics and the solvent comprises nitric acid and,if any support is present, another acid to dissolve any support (such ashydrofluoric acid to dissolve silica supports) is present;

(f) 35 weight percent or more high weight average molecular weightcomponent, as measured by size-exclusion chromatography, preferably 40%or more. In a particularly preferred embodiment the higher molecularweight fraction is present at between 35 and 70 weight %, morepreferably between 40 and 60 weight %.

Molecular weight (Mw and Mn) are measured as described below in theexamples section.

In another embodiment, the polymer product has a residual metal contentof 2.0 ppm transition metal or less, preferably 1.8 ppm transition metalor less, preferably 1.6 ppm transition metal or less, preferably 1.5 ppmtransition metal or less, preferably 2.0 ppm or less of group 4 metal,preferably 1.8 ppm or less of group 4 metal, preferably 1.6 ppm or lessof group 4 metal, preferably 1.5 ppm or less of group 4 metal,preferably 2.0 ppm or less zirconium, preferably 1.8 ppm or lesszirconium, preferably 1.6 ppm or less zirconium, preferably 1.5 ppm orless zirconium(as measured by Inductively Coupled Plasma OpticalEmission Spectroscopy run against commercially available standards,where the sample is heated so as to fully decompose all organics and thesolvent comprises nitric acid and, if any support is present, anotheracid to dissolve any support (such as hydrofluoric acid to dissolvesilica supports) is present.

In another embodiment, the polymer product has a residual nitrogencontent of 2.0 ppm or less, preferably 1.8 ppm nitrogen or less,preferably 1.6 ppm nitrogen or less, preferably 1.5 ppm nitrogen or less(as measured by Inductively Coupled Plasma Optical Emission Spectroscopyrun against commercially available standards, where the sample is heatedso as to fully decompose all organics and the solvent comprises nitricacid and, if any support is present, another acid to dissolve anysupport (such as hydrofluoric acid to dissolve silica supports) ispresent.

In another embodiment, the polymer produced herein has a compositiondistribution breadth index (CDBI) of 70 or more, preferably 75 or moreeven more preferably 80 or more. Composition distribution breadth indexis a means of measuring the distribution of comonomer between polymerchains in a given sample. CDBI is measured according to the procedure inWO 93/03093, published Feb. 18, 1993, provided that fractions having amolecular weight below 10,000 Mn are ignored for the calculation.

In a preferred embodiment, the polyolefin recovered typically has a meltindex as measured by ASTM D-1238, Condition E, at 190° C. of 3000 g/10min or less. In a preferred embodiment the polyolefin is ethylenehomopolymer or copolymer. In a preferred embodiment for certainapplications, such as films, molded article and the like a melt index of100 g/10 min or less is preferred. For some films and molded article amelt index of 10 g/10 min or less is preferred.

In another aspect, this invention relates to a polymer produced in asingle reactor having an I₂₁ of less than or equal to 20 g/10 min and anmelt index ratio (MIR=I₂₁/I₂) of greater than or equal to 80. I₂₁, andI₂ are measured according to ASTM 1238, condition E at 190° C.

In another aspect, this invention relates to films produced from thepolymer produced herein.

In a preferred embodiment, the catalyst system described above is usedto make a polyethylene having a density of between 0.94 and 0.970 g/cm³(as measured by ASTM 1505) and a melt index of 0.5 or less g/10 min orless (as measured by ASTM D-1238, Condition E, at 190° C.).

Polyethylene having a melt index of between 0.01 to 10 dg/min ispreferably produced.

Polyolefins, particularly polyethylenes, having a density of 0.89 to0.97 g/cm³ can be produced using this invention. In particularpolyethylenes having a density of 0.910 to 0.965, preferably 0.915 to0.960, preferably 0.920 to 0.955 can be produced. In some embodiments, adensity of 0.915 to 0.940 g/cm³ would be preferred, in other embodimentsdensities of 0.930 to 0.970 g/cm³ are preferred.

The melt index (and other properties) of the polymer produced may bechanged by manipulating the polymerization system by:

1) changing the amount of the first catalyst in the polymerizationsystem, and/or

2) changing the amount of the second catalyst in the polymerizationsystem, and/or

3) adding or removing hydrogen to or from the polymerization process;and/or

4) changing the amount of liquid and/or gas that is withdrawn and/orpurged from the process; and/or

5) changing the amount and/or composition of a recovered liquid and/orrecovered gas returned to the polymerization process, said recoveredliquid or recovered gas being recovered from polymer discharged from thepolymerization process; and/or

6) using a hydrogenation catalyst in the polymerization process; and/or

7) changing the polymerization temperature; and/or

8) changing the ethylene partial pressure in the polymerization process;and/or

9) changing the ethylene to comonomer ratio in the polymerizationprocess; and/or

10) changing the activator to transition metal ratio in the activationsequence, and/or

11) changing the length of time that activator contacts the transitionmetal in the activation sequence, and/or

12) varying the amount of the activator(s) and/or the two or morecatalysts that are introduced into the feed apparatus, and/or

13) altering the point at which the multiple catalysts and or activatorsare added to the feed apparatus, and/or

14) altering the residence times of the multiple catalysts in the feedapparatus, and/or

15) altering the flow rate of the carrier, and/or

16) altering the temperature of the mixture in the feed apparatus.

In a preferred embodiment the hydrogen concentration in the reactor isabout 200-2000 ppm, preferably 250-1900 ppm, preferably 300-1800 ppm,preferably 350-1700 ppm, preferably 400-1600 ppm, preferably 500-1500ppm, preferably 500-1400 ppm, preferably 500-1200 ppm, preferably600-1200 ppm, preferably 700-1100 ppm, more preferably 800-1000 ppm.

The polyolefins then can be made into films, molded articles (includingpipes), sheets, wire and cable coating and the like. The films may beformed by any of the conventional techniques known in the art includingextrusion, co-extrusion, lamination, blowing and casting. The film maybe obtained by the flat film or tubular process which may be followed byorientation in an uniaxial direction or in two mutually perpendiculardirections in the plane of the film to the same or different extents.Orientation may be to the same extent in both directions or may be todifferent extents. Particularly preferred methods to form the polymersinto films include extrusion or coextrusion on a blown or cast filmline.

The films produced may further contain additives such as slip,antiblock, antioxidants, pigments, fillers, antifog, UV stabilizers,antistats, polymer processing aids, neutralizers, lubricants,surfactants, pigments, dyes and nucleating agents. Preferred additivesinclude silicon dioxide, synthetic silica, titanium dioxide,polydimethylsiloxane, calcium carbonate, metal stearates, calciumstearate, zinc stearate, talc, BaSO₄, diatomaceous earth, wax, carbonblack, flame retarding additives, low molecular weight resins,hydrocarbon resins, glass beads and the like. The additives may bepresent in the typically effective amounts well known in the art, suchas 0.001 weight % to 10 weight %.

EXAMPLES

Mn and Mw were measured by gel permeation chromatography on a waters150° C. GPC instrument equipped with differential refraction indexdetectors. The GPC columns were calibrated by running a series ofmolecular weight standards and the molecular weights were calculatedusing Mark Houwink coefficients for the polymer in question.

MWD=M _(w) /M _(n)

Density was measured according to ASTM D 1505.

Melt Index (MI) I₂ was measured according to ASTM D-1238, Condition E,at 190° C.

I₂₁ was measured according to ASTM D-1238, Condition F, at 190° C.

Melt Index Ratio (MIR) is the ratio of I₂₁ over I₂.

Weight % comonomer was measured by proton NMR.

“PPH” is pounds per hour. “mPPH” is millipounds per hour. “ppmw” isparts per million by weight.

CATALYST 1

Indenyl zirconium tris pivalate, a bulky ligand metallocene-typecompound, also represented by formula VI, can be prepared by performingthe following general reactions:

Zr(NEt₂)₄+IndH→IndZr(NEt₂)₃+Et₂NH  (1)

IndZr(NEt₂)₃+3(CH₃)₃CCO₂H→IndZr[O₂CC(CH₃)]₃+Et₂NH  (2)

Where Ind=indenyl and Et is ethyl.

CATALYST 2

Preparation of [(2,4,6-Me₃C₆H₂)NHCH₂CH₂]₂NH Ligand (Ligand I)

A 2 L one-armed Schlenk flask was charged with a magnetic stir bar,diethylenetriamine (23.450 g, 0.227 mol), 2-bromomesitylene (90.51 g,0.455 mol), tris(dibenzylideneacetone)dipalladium (1.041 g, 1.14 mmol),racemic-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (racemic BINAP)(2.123 g, 3.41 mmol), sodium tert-butoxide (65.535 g, 0.682 mol), andtoluene (800 mL) under dry, oxygen-free nitrogen. The reaction mixturewas stirred and heated to 100 C. After 18 h the reaction was complete,as judged by proton NMR spectroscopy. All remaining manipulations can beperformed in air. All solvent was removed under vacuum and the residuesdissolved in diethyl ether (1 L). The ether was washed with water (3×250mL) followed by saturated aqueous NaCl (180 g in 500 mL) and dried overmagnesium sulfate (30 g). Removal of the ether in vacuo yielded a redoil which was dried at 70 C for 12 h under vacuum (yield: 71.10 g, 92%).¹H NMR (C₆D₆) δ 6.83 (s, 4), 3.39 (br s, 2), 2.86 (t, 4), 2.49 (t, 4),2.27 (s, 12), 2.21 (s, 6), 0.68 (br s, 1).

Preparation of Catalyst 2

Preparation of 1.5 wt % Catalyst A in Toluene Solution

Note: All procedures below were performed in a glove box.

1. Weighed out 100 grams of purified toluene into a 1 Erlenmeyer flaskequipped with a Teflon coated stir bar.

2. Added 7.28 grams of Tetrabenzyl Zirconium.

3. Placed solution on agitator and stirred for 5 minutes. All of thesolids went into solution.

4. Added 5.42 grams of Ligand I.

5. Added an additional 551 grams of purified toluene and allowed mixtureto stir for 15 minutes. No solids remained in the solution.

6. Poured catalyst solution into a clean, purged 1-L Whitey samplecylinder, labeled, removed from glovebox and placed in holding area foroperations.

Alternate Preparation of Compound I{[(2,4,6-Me₃C₆H₂)NCH₂CH₂]₂NH}Zr(CH₂Ph)₂

A 500 mL round bottom flask was charged with a magnetic stir bar,tetrabenzyl zirconium (Boulder Scientific) (41.729 g, 91.56 mmol), and300 mL of toluene under dry, oxygen-free nitrogen. Solid ligand I above(32.773 g, 96.52 mmol) was added with stirring over 1 minute (thedesired compound precipitates). The volume of the slurry was reduced to100 mL and 300 mL of pentane added with stirring. The solidyellow-orange product was collected by filtration and dried under vacuum(44.811 g, 80% yield). ¹H NMR (C₆D₆) δ 7.22-6.81 (m, 12), 5.90 (d, 2),3.38 (m, 2), 3.11 (m, 2), 3.01 (m, 1), 2.49 (m, 4), 2.43 (s, 6), 2.41(s, 6), 2.18 (s, 6), 1.89 (s, 2), 0.96 (s, 2).

Preparation of Catalyst 1

Preparation 1 wt % Catalyst 1 in Hexane Solution

All procedures were performed in a glove box.

1. Transfer 1 liter of purified hexane into a 1 L Erlenmeyer flaskequipped with a Teflon coated stir bar.

2. Add 6.67 grams of indenyl zirconium tris pivalate dried powder.

3. Place solution on magnetic agitator and stir for 15 minutes. All ofthe solids go into solution.

4. Pour solution into a clean, purged 1-L Whitey sample cylinder,labeled, and removed from glovebox and place in holding area until usein operation.

CATALYST 3

Catalyst 3 is [1-(2-Pyridyl)N-1-Methylethyl][1-N-2,6-DiisopropylphenylAmido] Zirconium Tribenzyl and was produced as follows:

Preparation Of[1-(2-Pyridyl)N-1-Methylethyl][1-N-2,6-Diisopropylphenyl]Amine

In a dry box, 22.45 mmol (6.34 g)2-acetylpyridine(2,6-diisopropylphenylimine) were charged to a 250 mLround bottom flask equipped with a stir bar and septa. The flask wassealed, removed from the dry box and placed under nitrogen purge. Drytoluene (50 mL) was added and stirred to dissolve the ligand. The vesselwas chilled to 0° C. in a wet ice bath. Trimethyl aluminum (Aldrich, 2.0M in toluene) was added dropwise over ten minutes. The temperature ofthe reaction was not allowed to exceed 10° C. When addition of thetrimethyl aluminum was complete, the mixture was allowed to warm slowlyto room temperature, and then was then placed in an oil bath and heatedto 40° C. for 25 minutes. The vessel was removed from the oil bath andplaced in an ice bath. A dropping funnel containing 100 mL of 5% KOH wasattached to the flask. The caustic was charged to the reaction dropwiseover a 1 hour span. The mixture was transferred to a separatory funnel.The aqueous layer was removed. The solvent layer was washed with 100 mLwater then 100 mL brine. The red-brown liquid product was dried overNa₂SO₄, vacuum stripped and placed under high vacuum over night.

80 mL of red-brown liquid was transferred to a 200 mL Schlenk flaskequipped with a stir bar. A distillation head with a dry ice condenserwas attached to the flask. The mixture was vacuum distilled yieldingapproximately 70 g of dark yellow viscous liquid product.

Preparation Of [1-(2-Pyridyl)N-1-Methylethyl][1-N-2,6-DiisopropylphenylAmido] Zirconium Tribenzyl

In a darkened room and darkened dry box, 5.0 mmol (1.45 g) of the ligandmade in Example 1 were charged to a 100 mL Schlenk tube equipped with astir bar. The ligand was dissolved in 5 mL of toluene. To a secondvessel equipped with a stir bar was charged 5.5 mmol (2.5g) tetrabenzylzirconium and 10 mL toluene.

The ligand solution was transferred into the tetrabenzyl zirconiumsolution. The vessel was covered with foil and allowed to stir at roomtemperature in the dry box. After 6 hours at room temperature 80 mL dryhexane was added to the reaction solution and allowed to stir overnight.The reaction mixture was filtered through a medium porosity frit withapproximately 2 g pale yellow solids collected.

CATALYST 4

Catalyst 4 is tetrahydroindenyl zirconium tris pivalate, a bulky ligandmetallocene-type compound, also represented by formula VI, can beprepared by performing the following general reactions:

Zr(NEt₂)₄+IndH→IndZr(NEt₂)₃+Et₂NH  (1)

IndZr(NEt₂)₃+3(CH₃)₃CCO₂H→IndZr[O₂CC(CH₃)]₃+Et₂NH  (2)

Where Ind=tetrahydroindenyl and Et is ethyl.

Example 1

An ethylene hexene copolymer was produced in a 14-inch (35.6 cm) pilotplant scale gas phase reactor operating at 85° C., and 350 psig (2.4MPa) total reactor pressure having a water cooled heat exchanger. Thereactor was equipped with a plenum having about 1,600 PPH of recycle gasflow. (The plenum is a device used to create a particle lean zone in afluidized bed gas-phase reactor. See U.S. Pat. No. 5,693,727.) A taperedcatalyst injection nozzle having a 0.041 inch (0.10 cm) hole size wasposition in the plenum gas flow. Prior to starting the catalyst feed,ethylene pressure was about 220 psia (1.5 MPa), 1-hexene concentrationwas about 0.6 mol % and hydrogen concentration was about 0.25 mol %.Nitrogen was fed to the reactor as a make-up gas at about 5-8 PPH. Thecatalyst solution was a 1:1 molar ratio of Catalyst 3:Catalyst 4catalyst in a toluene solution. Catalyst feed was started at 13 cc's perhour, which was sufficient to give the desired production rate of 17lbs/hr(kg/hr7.7). The catalyst and co-catalyst (MMAO-3A, 1 wt %Aluminum) were mixed in line prior to passing through the injectionnozzle into the fluidized bed. MMAO to catalyst was controlled so thatthe Al:Zr molar ratio was 300:1. 5.0 lbs/hr (2.3 kg/hr) Nitrogen and 20lbs/hr (9.1 kg/hr) 1-hexene were also fed to the injection nozzle. Abimodal polymer having nominal 0.43 dg/min (I₂₁) and 0.942 g/ccproperties was obtained. The resin average particle size was 0.023inches (0.58 cm). A residual zirconium of 2.2 ppmw was measured by x-rayfluorescence.

Example 2

An ethylene hexene copolymer was produced in a 14-inch pilot plant scalegas phase reactor operating at 85° C. and 350 psig (2.4 MPa) totalreactor pressure having a water cooled heat exchanger The reactor wasequipped with a plenum having about 1,600 PPH of recycle gas flow. (Theplenum is a device used to create a particle lean zone in a fluidizedbed gas-phase reactor. See U.S. Pat. No. 5,693,727.) A tapered catalystinjection nozzle having a 0.055 inch (1.4 cm) hole size was position inthe plenum gas flow. Prior to starting the catalyst feed, ethylenepressure was about 220 psia (1.5 MPa), 1-hexene concentration was about0.3 mol % and hydrogen concentration was about 0.12 mol %.

Catalyst 2 was dissolved in a 0.5 wt % solution in toluene and was fedto reactor at 12 cc/hr. MMAO-3A, 1 wt % Aluminum) co-catalyst was mixedwith the Catalyst 2 in the feed line prior to the reactor at a molarratio of 400:1 Al/Zr. The production rate was about 24 lb/hr(10.9kg/hr).In addition, 5.0 lbs/hr (2.3 kg/hr) Nitrogen and 0.1 lbs/hr(0.05 kg/hr)1-hexene and 0.2 lb/hr (0.09 kg/hr) isopentane were also fed to theinjection nozzle. The polymer had a flow index of 0.31 and a density of0.935 g/cc. After this was established, the catalyst feed rate wasreduced to 6 cc/hr of catalyst 2 and a 0.125 wt% Catalyst 1 in hexanesolution feed was added to the injection line at 13 cc/hr. The entireorder of addition was the hexene and the MMAO mixed with the Catalyst 1,Catalsyt 2 solution was added, then isopentane and nitrogen. The Al/Zrfor the entire system was about 500. Within 6 hours of the addition ofCatalyst 1, the bimodal polymer had a nominal 12.9 dg/min (I₂₁), a 130MFR(melt flow ratio I₂₁/I₂)and 0.953 g/cc density. The resin averageparticle size was 0.0479 inched (0.12 cm). A residual zirconium of 0.7ppmw was measured by x-ray fluorescence.

Example 3

—Three Catalyst Component Examples:

Example A. Preparation of a Two-catalyst Component Solution

1. In a glovebox, weighed out 688.4 g of purified toluene into a 1 LErlenmeyer flask equipped with a Teflon coated stirbar.

2. Added 3.45 g of Catalyst 3 catalyst and 0.43 g of bisn-butylcyclopentadienyl zirconium dichloride, placed on agitator andstirred for 15 minutes. All solids went into solution.

3. Charged 1 L of catalyst solution to a Whitey samplecylinder,.labeled, removed from glovebox and placed into holding areafor operations.

Example B. Preparation of Third Catalyst Component Solution

1. In a glovebox, weighed out 647 g of purified hexane into a 1 LErlenmeyer flask equipped with a Teflon coated stirbar.

2. Added 0.81 g of indenyl zirconium tris-pivalate catalyst from BoulderScientific, placed on agitator and stirred for 15 minutes. All solidswent into solution.

3. Charged 1 L of catalyst solution to a Whitey sample cylinder,labeled, removed from glovebox and placed into holding area foroperations.

Example C. Production of Resin Containing Three Catalyst ComponentsUCUT-1507-58 Drums 92-94

An ethylene hexene copolymer was produced in a 14-inch (35.6 cm) pilotplant scale gas phase reactor operating at 85° C. and 350 psig (2.4 MPa)total reactor pressure having a water cooled heat exchanger. Ethylenewas fed to the reactor at a rate of about 38 pounds per hour (17.2kg/hr), hexene was fed to the reactor at a rate of about 0.3 pounds perhour (0.14 kg/hr) and hydrogen was fed to the reactor at a rate of 8mPPH. Nitrogen was fed to the reactor as a make-up gas at about 4-8 PPH.The production rate was about 30 PPH. The reactor was equipped with aplenum having about 1,600 PPH of recycle gas flow. (The plenum is adevice used to create a particle lean zone in a fluidized bed gas-phasereactor. See U.S. Pat. No. 5,693,727.) A tapered catalyst injectionnozzle having a 0.055 inch (0.14 cm) hole size was position in theplenum gas flow. Catalyst from Example B was contacted in-line with1-hexene and 3.55% Al (MMAO-3A) in hexane for approximately 30 minutesbefore joining a stream of the mixed catalyst from Example A. Thecatalyst ratio was kept at 2.2:1 (Example B: Example A). The MMAO-3A wascontrolled so that the overall Al:Zr molar ratio was 230:1. Nitrogen wasalso fed to the injection nozzle as needed to maintain a stable averageparticle size.

A broad molecular weight distribution polymer having nominal 4.69 dg/minI₂₁, 0.02 dg/min, 234 I₅/I₂₁ ratio and 0.948 g/cc properties wasobtained. A residual zirconium of 1.18 ppmw was calculated based on areactor mass balance. The polymer was characterized by SEC (See FIG. 1)and determined to be approximately 53% high molecular weight polymer.The final polymer had an Mn of 12,222, an Mw of 372,661 and an Mw/Mn of30.49.

All documents described herein are incorporated by reference herein,including any priority documents and/or testing procedures. As isapparent form the foregoing general description and the specificembodiments, while forms of the invention have been illustrated anddescribed, various modifications can be made without departing from thespirit and scope of the invention. Accordingly it is not intended thatthe invention be limited thereby.

What is claimed is:
 1. A method to polymerize olefins in a gas-phasereactor comprising introducing a first catalyst, a second catalyst, andat least one activator into the reactor in a liquid carrier, wherein thefirst catalyst is structurally different from the second catalyst,wherein each catalyst is activated independently without having tocompete for the at least one activator, and wherein the first catalyst,the second catalyst and the activator(s) are combined in the liquidcarrier before being introduced into the reactor.
 2. The method of claim1 wherein the catalysts are activated sequentially.
 3. The method ofclaim 1 wherein the catalysts are combined in a liquid carrier thenintroduced into a channeling means connecting to the reactor andthereafter the activator(s) is introduced into the channeling means atthe same or different point as the catalysts.
 4. The method of claim 1wherein the catalysts are combined in a liquid carrier and thereafterthe activator(s) is introduced into the liquid carrier.
 5. The method ofclaim 4 wherein the liquid carrier containing the catalysts and theactivator(s) is placed into an apparatus for introducing the liquidcarrier into the reactor.
 6. The method of claim 5 wherein the catalystsand liquid carrier are introduced into the apparatus before theactivator is introduced into the apparatus.
 7. The method of claim 6wherein the liquid carrier is introduced into the reactor as a stream orspray.
 8. The method of claim 1 wherein at least one catalyst, at leastone activator and the liquid carrier are placed into an apparatus forintroduction into the reactor wherein additional catalyst(s) is/areintroduced into the apparatus after the first catalyst and activator areintroduced into the apparatus.
 9. The method of claim wherein a firstcombination comprising at least one catalyst in a liquid carrier isintroduced into an apparatus connecting to the reactor, and a secondcomposition comprising at least one activator in liquid carrier isintroduced into the apparatus connecting to the reactor, then, after aperiod of time, a different catalyst in liquid carrier is introducedinto the apparatus connecting to the reactor, and then thecatalyst-activator combination is introduced into the reactor.
 10. Themethod of claim 1 wherein at least one catalyst(a) and at least oneactivator(a) are combined in a liquid carrier, and at least onecatalyst(b) and at least one activator(b) are combined in a liquidcarrier, wherein the catalyst(b) is different from the catalyst(a)and/or the activator (b) is different from the activator(a), thereafterboth combinations are introduced into an apparatus connecting to thereactor, and, thereafter the combinations are introduced into thereactor.
 11. The method of claim 10 wherein the liquid carriercontaining catalyst(b) and activator(b) is introduced into the apparatusconnecting to the reactor after the liquid carrier containingcatalyst(a) and activator(a) is introduced into the apparatus connectingto the reactor.
 12. The method of claim 1 wherein: a first compositioncomprising at least one catalyst(a), at least one activator(a) and aliquid carrier is placed in an apparatus connected to the reactor, and asecond composition comprising at least one catalyst(b), at least oneactivator(b) and a liquid carrier, wherein the catalyst(b) and/or theactivator (b) is different from the catalyst(a) and/or the activator(a),is introduced into the apparatus connecting to the reactor after thefirst composition is placed into the apparatus, and thereafter thecombined compositions is introduced into the reactor.
 13. The method ofclaim 1 wherein at least one catalyst and the liquid carrier are placedinto an apparatus for introduction into the reactor wherein additionalcatalyst(s) and activator(s) are introduced into the apparatus after thefirst catalyst is introduced into the apparatus.
 14. The method of claim1 wherein: a first composition comprising at least one catalyst(a), atleast one activator(a) and a liquid carrier is introduced into anapparatus feeding into a reactor, and thereafter a second catalyst in aliquid carrier is added to the apparatus feeding into the reactor, andthereafter a second activator in a liquid carrier is added to theapparatus feeding into the reactor, and thereafter the total combinationis introduced into the reactor.
 15. The method of claim 1 wherein afirst catalyst is a bulky ligand metallocene type catalyst and a secondcatalyst is a group 15 containing compound.